CN109904498B - Mineral material electrolyte for low-temperature solid oxide fuel cell - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本发明公开了一种用于低温固体氧化物燃料电池的矿物材料电解质，它以赤铁矿和Ce0.9Gd0.1O1.95粉为主要原料制备而成。本发明首次提出将天然赤铁矿与GDC粉末复合制备矿物材料电解质，可同时克服天然赤铁矿与GDC电化学性能的不足，有利于提升所得固体氧化物燃料的电化学性能，且所得复合电解质可使SOFC在低温下呈现优异的电化学性能，有效拓宽现有固体氧化物燃料电池的适用领域，具有重要的研究和推广价值；此外，该矿物材料电解质涉及的合成工艺简单、成本低廉、生产效率高，适合推广应用。
The invention discloses a mineral material electrolyte for low-temperature solid oxide fuel cells, which is prepared by using hematite and Ce 0.9 Gd 0.1 O 1.95 powder as main raw materials. The invention proposes for the first time that natural hematite and GDC powder are compounded to prepare a mineral material electrolyte, which can simultaneously overcome the shortcomings of the electrochemical properties of natural hematite and GDC, and is beneficial to improve the electrochemical properties of the obtained solid oxide fuel, and the obtained compound electrolyte It can make SOFC show excellent electrochemical performance at low temperature, effectively broaden the applicable field of existing solid oxide fuel cells, and has important research and promotion value; in addition, the mineral material electrolyte involves a simple synthesis process, low cost, and production High efficiency, suitable for promotion and application.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a low-cost mineral material electrolyte for a low-temperature solid oxide fuel cell.
Background
In the modern society, the energy crisis and the environmental pollution have become the focus of attention in all countries of the world. At present, the dominant fossil energy is limited in reserves and non-renewable, and meanwhile, a large amount of harmful gas is emitted by combustion of the fossil energy, so that the fossil energy is an important cause of environmental pollution problems such as greenhouse effect and haze, and serious harm is brought to social development and human life. Therefore, developing new green, environment-friendly and sustainable energy, and optimizing the use mode and use efficiency of fossil energy have become important problems to be solved urgently.
Solid Oxide Fuel Cells (SOFC) are important energy conversion devices that utilize chemical reactions to store H2Or the chemical energy in the hydrocarbon fuel is directly converted into electrical energy. The SOFC main component comprises an electrolyte, and a cathode and an anode which are respectively positioned on two sides of the electrolyte; the SOFC can adopt various fuels such as hydrogen, hydrocarbon, biomass, coal and the like, and has high energy conversion rate; and is mainly used during workingThe emission to be treated is water with CO2And the emission amount of other pollutants is very low, the method can solve the problems of the current energy crisis, environmental pollution and the like, and is a clean energy technology with wide application prospect.
However, for SOFCs, challenges from high cost and short operating life need to be addressed to achieve large scale applications. In order to reduce costs and extend operational life, it is effective to reduce operating temperatures and use conventional materials for SOFC components. However, Ce is frequently used at present once the SOFC operation temperature is lowered0.9Gd0.1O1.95(GDC) and the like can not meet the performance requirements of the SOFC, so that the further development of a novel electrolyte material with reliable performance and capable of maintaining excellent electrochemical performance under a low-temperature condition is a hot spot problem in the low-temperature process of the SOFC at present.
Disclosure of Invention
The invention mainly aims to provide a mineral material electrolyte for a low-temperature solid oxide fuel cell, aiming at the defects in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a mineral electrolyte for low-temp solid oxide fuel cell is prepared from hematite and Ce0.9Gd0.1O1.95Mixing the components.
In the above scheme, the hematite and Ce are0.9Gd0.1O1.95The mass ratio of the powder is 1: 1.
In the scheme, the hematite is natural hematite, wherein the main chemical component is Fe2O3The oxide mineral belongs to a hexagonal system, and comprises the following main components in percentage by weight: fe2O3 70～90wt％，SiO23-8 wt%; further contains Al2O3And trace components such as CaO, MgO, and CuO.
The preparation method of the mineral material electrolyte for the low-temperature solid oxide fuel cell comprises the following steps:
1) calcining and ball-milling the hematite in sequence to obtain hematite powder;
2) mixing the obtained hematite powder with Ce0.9Gd0.1O1.95Mixing the powder in proportion, and ball-milling uniformly to obtain mixed powder;
3) and pressing and sintering the obtained mixed powder to obtain the compact mineral material electrolyte (mixed electrolyte substrate).
In the scheme, the calcining temperature is 700-900 ℃, and the time is 2-4 h.
In the scheme, the sintering temperature is 1200-1300 ℃, and the time is 4-5 h.
The principle of the invention is as follows:
the invention prepares the mineral material electrolyte by compounding natural hematite and GDC powder, wherein the hematite semiconductor is gamma-Fe2O3With insulator SiO2The composite action of the interface and the carbonate can generate a high ion conduction path at the phase interface, so that the hematite and the GDC generate high ion conductivity at the phase interface when being mixed, the obtained mixed electrolyte is promoted to show excellent ion conduction capability, the defects of the electrochemical performance of a single natural hematite and GDC material can be overcome, and the electrochemical performance of the obtained solid oxide fuel can be improved; in addition, the internal crystal structure of natural hematite contains various trace components (Al)2O3CaO, MgO, CuO, etc.), which are beneficial to provide better hole transport capability and higher ion conductivity, and the minerals also have good band gap structure and good stability, which is beneficial to further ensure the stability of the obtained electrolyte material, etc.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly proposes that the natural hematite and the GDC powder are compounded to prepare the mineral material electrolyte, can overcome the defects of the electrochemical properties of the natural hematite and the GDC, and the obtained composite electrolyte can enable the SOFC to present excellent electrochemical properties at low temperature, effectively broadens the application field of the existing solid oxide fuel cell, and has important research and popularization values.
2) The synthesis process provided by the invention is simple, low in cost and high in production efficiency, can effectively reduce the manufacturing cost of the SOFC, can further improve the electrochemical performance of the obtained electrolyte material, and has remarkable economic benefit.
Drawings
FIG. 1 is a schematic view showing oxygen ion and electron conduction inside the half cell obtained in example 1.
Fig. 2 is an XRD spectrum of the mineral material electrolyte substrate obtained in example 1.
FIG. 3 is an XRD pattern of a mixed powder obtained by roasting hematite powder and LNO powder at 900 ℃ for 2 hours.
FIG. 4 is a graph of the thermal expansion of the hematite in example 1 over a temperature range of 40-1000 ℃.
Fig. 5 is a schematic diagram of a half cell structure adopted by the three-electrode test system.
FIG. 6 is a diagram of EIS of a half cell prepared using the electrolyte substrate obtained in example 1.
Fig. 7 is an EIS diagram of a half cell fabricated using the electrolyte substrate obtained in comparative example 1.
Fig. 8 is an EIS diagram of a half cell fabricated using the electrolyte substrate obtained in comparative example 2.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, hematite used was provided by the molybdenum industry, wherein the main components and their mass percentages included: fe2O3 86.143％、SiO2 5.552％、Al2O3 1.522％、CaO 0.525％、MgO 0.324％、CuO 0.18％。
In the following examples, the preparation method of LNO cathode slurry used includes the following steps:
1) according to La2NiO4+δStoichiometric amount of La (NO)3)3·6H2O and Ni (NO)3)2·6H 20, dissolving the mixture in sufficient deionized water, and uniformly stirring to form a mixed solution of metal nitrate; then adding a certain amount of citric acid C6H8O7·H2O (controlling the molar ratio of citric acid to metal ions to be 1.1:1), heating the obtained mixed solution to 80 ℃, carrying out oil bath stirring for 2h, then heating to 120 ℃ to obtain light green gel, then placing the gel in an electrothermal blowing drying oven for drying at 120 ℃ for 5h to obtain a black precursor, and finally placing the black precursor in a muffle furnace for calcining at 1000 ℃ for 8h to obtain black La2NiO4+δPowder (LNO powder);
2) mixing the obtained LNO powder with a binder (prepared by mixing dibutyl phthalate, n-butyl alcohol, terpineol and ethyl cellulose according to a mass ratio of 24:7:60: 9) according to a mass ratio of 6:4, placing the mixture in a mortar, and manually grinding the mixture for 1 hour to prepare LNO cathode slurry with certain fluidity.
Example 1
A mineral material electrolyte for a low-temperature solid oxide fuel cell is prepared by the following steps:
1) placing natural Hematite (HEM) in a crucible, and calcining at 700 ℃ in an air atmosphere for 2 h; then, ball-milling the calcined hematite in a ball mill for 48 hours to reduce the particle diameter of the powder (about 200-500 nm) and obtain hematite powder with uniform fineness;
2) mixing the obtained hematite powder with Ce0.9Gd0.1O1.95Mixing the powder according to the mass ratio of 1:1, and uniformly ball-milling to obtain mixed powder;
3) placing 2g of the obtained mixed powder in a cylindrical die with the diameter of 26mm, uniformly pressurizing to 10MPa under a press machine, maintaining the pressure for 1min, then releasing the pressure, and demoulding to obtain a circular biscuit; and finally, placing the biscuit in a high-temperature muffle furnace, and sintering in air at 1250 ℃ for 4h to obtain the compact mineral material electrolyte substrate with the diameter of 20mm and the thickness of 0.8 mm.
FIG. 1 is a graph showing oxygen ion and electron conductivities inside a half cell with a mixed hematite and GDC in a mass ratio of 1:1 and LNO as a cathode obtained in this example, in which hematite containing Mg, Al and Cu shows a high conductivity mainly due to an increase in the number of internal hole carriers, and in which 86.143% of semiconductor gamma-Fe is contained in the main component inside hematite2O3To 5.552% insulatorSiO2The interface between hematite and GDC, the interface between hematite and GDC and the inside of GDC all generate high ion conduction path, so that the obtained mixed electrolyte shows excellent ion conduction capability.
Fig. 2 is an XRD spectrum of the mineral material electrolyte substrate obtained in this example, in which only characteristic diffraction peaks of each original component are present and no other miscellaneous peaks are present, and no positional shift of the characteristic diffraction peaks is found when comparing the positions of the characteristic diffraction peaks of the mixed powder and the original powder. Indicating that neither chemical reaction nor element interdiffusion occurs between GDC and HEM in the roasting process; GDC and HEM have good chemical compatibility as a mixed electrolyte.
FIG. 3 is an XRD (X-ray diffraction) spectrum of a mixed powder obtained by roasting hematite powder and LNO powder at 900 ℃ for 2 hours, wherein only characteristic diffraction peaks of each original component are contained in the spectrum, no other miscellaneous peaks appear in the spectrum, and no position deviation of the characteristic diffraction peaks is found by comparing the positions of the characteristic diffraction peaks of the mixed powder and the original powder; indicating that no chemical reaction or mutual diffusion of elements occurs between LNO and HEM in the roasting process; the LNO and the HEM have good chemical compatibility as a mixed electrolyte.
Weighing 1.5g of hematite powder, placing the hematite powder in a mold, uniformly pressurizing to 8MPa under a press machine, maintaining the pressure for 1 minute, then releasing the pressure, and demolding to obtain a cuboid biscuit; then, the substrate was sintered in a high temperature muffle furnace at 1150 ℃ for 5 hours to obtain a compact rectangular parallelepiped substrate, and the thermal expansion property was measured (see the result in FIG. 4). Performing linear fitting on a thermal expansion curve of the hematite within a temperature range of 40-1000 ℃ to obtain the hematite with the thermal expansion coefficients of 11.83 multiplied by 10-6K-1The thermal expansion coefficient of GDC is 12.23 × 10 within 40-1000 deg.C-6K-1The thermal expansion coefficient of LNO is 14.3X 10-6K-1The thermal expansion coefficients of hematite, LNO and GDC are close to each other, so that the hematite, LNO and GDC have good thermal matching performance within the temperature range of 40-1000 ℃, and the long-term stable operation of the battery with LNO as a cathode material and HEM-GDC as a composite electrolyte can be guaranteed.
Comparative examples 1 to 2
Comparative examples 1 and 2 each using pure Ce0.9Gd0.1O1.95The method for preparing the electrolyte substrate by using the powder and the hematite powder comprises the following specific steps of: 2g of GDC (Ce) was weighed out separately0.9Gd0.1O1.95Powder) and hematite powder are placed in a cylindrical die with the diameter of 26mm, the pressure is uniformly increased to 10MPa under a press machine, the pressure is maintained for 1min, the pressure is relieved, and a circular biscuit is obtained after demoulding; and then placing the substrate in a high-temperature muffle furnace, and sintering the substrate in air at 1550 ℃ for 5 hours and in air at 1150 ℃ for 4 hours respectively to obtain a compact GDC electrolyte substrate with the diameter of 22mm and the thickness of 0.9mm and a compact hematite electrolyte substrate with the diameter of 19mm and the thickness of 0.7 mm.
The mineral material electrolyte substrate obtained in example 1, the GDC electrolyte substrate obtained in comparative example 1, and the hematite electrolyte substrate obtained in comparative example 2 were used in combination with LNO cathode materials, respectively, to prepare a half cell, and the specific steps included the following:
1) LNO cathode pastes were printed on the electrolyte substrates obtained in example 1, comparative example 1 and comparative example 2, respectively, by screen printing (at the working electrodes shown in fig. 5);
2) respectively transferring the samples printed in the step 1) to a medium-temperature muffle furnace, and roasting for 2 hours in the air at 900 ℃ to firmly combine the cathode material with the electrolyte substrate;
3) printing platinum paste on the counter electrode and the reference electrode of the electrolyte substrate; and then respectively moving the obtained samples to a medium-temperature muffle furnace, and roasting for 2 hours in air at 900 ℃ to firmly combine platinum with the electrolyte substrate, thus obtaining the corresponding half cell.
The half-cells prepared using the electrolyte substrates obtained in example 1, comparative example 1 and comparative example 2 were subjected to electrochemical tests, and the results are shown in fig. 6, fig. 7 and fig. 8, respectively.
FIG. 6 is an EIS of a half cell having an ohmic resistance ratio of 13.82. omega. cm at 450, 500, 550 and 600 ℃ prepared by using the electrolyte substrate obtained in example 1 of the present invention-2、9.03Ω·cm-2、7.11Ω·cm-2And 4.85. omega. cm-2Polarization impedance of which is dividedRespectively 38.65 omega cm-2、10.87Ω·cm-2、1.80Ω·cm-2And 0.10. omega. cm-2(ii) a The total impedance values are 52.47 omega cm-2、16.14Ω·cm-2、8.91Ω·cm-2And 4.95. omega. cm-2。
FIG. 7 is an EIS of a half cell having an ohmic resistance ratio of 4.29. omega. cm at 450, 500, 550 and 600 ℃ prepared by using the electrolyte substrate obtained in comparative example 1-2、3.34Ω·cm-2、2.83Ω·cm-2And 2.38. omega. cm-2The polarization impedances of the two electrodes are respectively 110.01 omega cm-2、34.98Ω·cm-2、15.40Ω·cm-2And 6.44. omega. cm-2(ii) a The total impedance values are 114.30 omega cm-2、38.32Ω·cm-2、18.23Ω·cm-2And 9.23. omega. cm-2。
FIG. 8 is an EIS of a half cell having an ohmic resistance ratio of 62.20. omega. cm at 450, 500, 550 and 600 ℃ prepared by using the electrolyte substrate obtained in comparative example 2-2、36.00Ω·cm-2、19.96Ω·cm-2And 10.59. omega. cm-2Polarization impedances of 44.30 Ω · cm, respectively-2、12.20Ω·cm-2、1.62Ω·cm-2And 0.48. omega. cm-2(ii) a The total impedance values are 106.50 omega cm-2、48.20Ω·cm-2、21.58Ω·cm-2And 12.21. omega. cm-2. In comparison, at the same temperature, the polarization impedance of the half cell using hematite as the electrolyte is reduced to a certain extent compared with the half cell prepared by using the electrolyte substrate obtained by the invention, but the ohmic impedance and the total impedance value are greatly increased, the adoption of single hematite as the electrolyte material is not beneficial to ensuring the electrochemical performance of the obtained solid oxide fuel cell, and in addition, the pure hematite has slightly high electronic conductivity and can cause adverse consequences such as cell leakage and the like.
The test results show that: at the same temperature, the polarization impedance of the half cell of the novel mixed electrolyte material prepared by compounding hematite and GDC is far less than that of the half cell taking GDC as electrolyte, and the ohmic impedance is slightly greater than that of the half cell taking GDC as electrolyte; the ohmic impedance of the half cell of the novel mixed electrolyte material prepared by compounding the hematite and the GDC is far smaller than that of the half cell prepared by taking the hematite as an electrolyte, and the polarization resistance is slightly higher than that of the half cell prepared by taking the hematite as the electrolyte; in summary, the total impedance of the half cell adopting the mixed electrolyte material obtained by hematite and GDC is far less than that of the half cell prepared by taking GDC or hematite as a single material as an electrolyte, because the ionic conductivity of the mixed material at low temperature is higher than that of pure GDC and pure hematite, and the electronic conductivity is very low, the mixed material is very suitable for the low-temperature SOFC electrolyte, and the composite electrolyte obtained by uniformly mixing hematite and GDC according to the mass ratio of 1:1 can enable the SOFC to show excellent electrochemical performance at low temperature.
The novel mixed electrolyte prepared by mixing the natural hematite and the GDC can effectively overcome the defects of the natural hematite and the GDC and can obviously improve the electrochemical performance of the SOFC at low temperature; the composite material has the advantages of simple synthesis process, low cost and high production efficiency, can effectively reduce the manufacturing cost of the SOFC, effectively broadens the application field of the existing solid oxide fuel cell, and has important research and popularization values.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
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| CN114464857A (en) * | 2022-01-26 | 2022-05-10 | 湖北大学 | Natural hematite-imitated electrolyte and natural hematite-imitated electrolyte fuel cell |
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